Compounds containing both B–O and P–O groups are of wide interest and have been classified into borophosphates and borate–phosphates by R. Kniep et al. In addition to the B/P ratio, analysis results show that regulating the [M/(B+P)] ratio is also an effective strategy to synthesize new borate–phosphates. The first lithium lead borate–phosphate, LiPb4(BO3)(PO4)2, was synthesized by regulating this ratio. This compound crystallizes in the orthorhombic space group Pbca (No. 61). It possesses a 3D structure with a corrugated 2D layer of [B2Pb8O18]∞ that is further connected by a [LiP2O8]∞ chain; both BO3 and PO4 were isolated. First-principle theoretical studies were performed to aid the understanding of the electronic structures and the linear optical properties. In addition, thermal analysis, IR spectroscopy, and UV/Vis/NIR diffuse reflectance spectroscopy were performed on the reported material.